Halogenation of cyclic compounds



Patented Aug. `29,1933

, HALOGENATION- F cromo ooMPoUNns .Max 'Albert Kunz, Mannheim, and KarlKoeberle and Erich Berthold,Ludwigshafenon-the-Rhine, Germany, assignorsto General. A niline'Works,Inc., New York,.N. Y.',a ,cor-

l v g A poration of Delaware No VDrawing'. Application 'March' 8,Y1,929,*Serial No,`345`,'58'1 and in Germany October 19, 1928 n 1o'claims. (o1. 26o-s1) The present invention relates to the halogenationvof aromatic compounds 'by'means of halogen hydrides. .L Y

' We have found that one or several hydrogen atoms attached to thenucleus of a cyclic, .that is hydroaromatic orv aromatic` compoundvcanbe replaced by thesameorsdiierent halogens by acting on the saidcompound 'with 'halogen h ydride in an acid-selected from the Vgroupcon# sisting `of oleum, chlorosulphonic acid and'mix# tures of theseacids, in the presence of a halogen carrier. The term` halogen when'used in the description and the appen'dedfclaims is meant to comprisethe halogens, chlorine, bromineland iodine. The usual halogen carriersmaybe em.-

ployed .for the halogenation, particularly suitable are, for instance,sulphur, iodine, antimony, arsenic, bismuthand mercury andA compoundsthereof, such as the amalgams, of which up to YaboutlO per cent byweight calculated on the amount of the substance subjected toLhalogenation are to be employed. The exact amount to be taken depends'on the, eiiiciency off the halogen transferrer and the reactivity ofthe substance to be halogenated. f

Since the process isapplicable to all. cyclic, hydro-aromatic as Well asaromatic. compounds, and among the latter to isocyolic 'as Wellasheterocyclic compounds, a denite range offtemperature necessary forcarrying out halogenation by means of halogen hydridescannot bef-given,Gerierally speaking, the temperaturesfto `be ernployed are thoseappliedwhenhalogenating the substances in theusual manner byrn'eans Vofthe free halogens; thus, in many instances, halogena-l tion alreadyoccurs at ordinarytemperature." The vtemperature at which the reactionis to be carriedl out also dependsjon theamountandithe kind of halogentransferrer added." Higher temperatures are to` be applied'in casethehalogenationis carf ried out in oleum containing'only a'few per centof sulphur trioxide. ,Since the'acids employed are; capable of oxidizingthe substances under treatment, or otherwise reacting therewith," forinstancewith the formation of sulphonic acids, the temperatures shouldbe so' chosen as to avoid vsuch undesired reactions.Insorne-casealhowever, such secondary reactions are evenldesired, forinstance, when it is intended to prepare halogenatcdsolphonic acids of`aromatic hydrocar-V bons, such as chlorinated naphthalene sulphonicacids and the like, or tojproduce quinones. Thus for example, fwhen"brominating perylene lin chlorosulphonic acid in the presence ofiodine, brominated perylenequinone is directly obtained,

Y' According to our invention allV cyclic com? pounds can behalogenated. L VThe `more speciiic term aromatic compounds comprises, asstated above, isocyclic as well as heterocyclic compounds,

`Afor instance', hydrocarbons, suchl as benzene,

naphthalenc, anthracene, pyrene, 'perylena their homologues andsubstitution products, for in eo. Y

stance,` their nitro, aminoja'nd halogen derivai tives. `ol'curthermore,oxygen containing aromatic vdianthrones, such as ms-benzdianthrones,ymsnaphthodianthrones, allo-A ms naphthodian'- thrones,msfanthradianthrones, anthanthrones and the like, ordibenzpyrenequinones, or comf pounds which are isomeric to the aforesaidsubstances.. Likewise, `heterocyclicV compounds canv 7.5 l cording toour invention, for example, azines, ac- 1 s 1 ridones, lacridines,tliioindigo,` pyrazolanthrone, x j `qu1no11ne, pyridine, thioacridones,Coeramidobehalogenatcd by meansof` halogen hydrides 'ac-1 nines landsubstitution products thereof.

fThe' hologenation `of vcyclicv compounds by-1 means of halogen hydridesin the mannendescribedfproceeds vin most cases about quanti- .tatively,and' is therefore f of. particular, interest when compounds of acertainstage of halogenation are to be produced. 'Moreoventhe processprovides a method for perfectly utilizing halogen dition of salts ofthehalogen hydrides to be em` plOye'd,VV such as alkali metal salts, forexample .sodium chloride, sodium bromide, or potassium iodide. Y,

'hydrides obtained.as wastegasesxin many,p rofl A 'cesses inthe chemicalindustry. l It fis,'how`ever,. not necessary to introduce the halogenhydrides Several,differentlhalogens Vcan of course. be in;` o troducedin to the cyclic compounds.accordingA to v Vour-invention invoneoperationby, employing dif-v ferent halogen hydrides or thecorrespondingal# kali metal saltsf.

The processiel of particular advantageior'the Y i halogenation yofp'olynuclear aromatic compounds, 5 Y

also such as contain a-carbonylgroup, as it provides anV economic Vwayof producing valuable/in# tcl-mediate-.products for, o the preparationof dye-I i stuis, or in casethe aromatic'polynuclear com-.- poundscontain groups capable of..being vatted for the ,production Vof vatdyestuiiswhicn may ence of iodine yields brominated perylenequinone.

Particularly valuable newrvat dyestufs which can be produced accordingto our invention are the monohalogen derivativesv of mcnoalkyl'ethers ofanthanthrone in whichfthe alkyl group'rnayY further be substituted. Thedyeings obtained therewith on cotton aref distinguished;by their;excellent fastness to lightl and 'to atmospheric in?vv iuences. y

The following exampleswill AJfurther' illustrate the nature ofv ourinvention, but the invention is,

not restricted thereto. The parts are by weight.

Example-1 Y y l 46 parts of' dibenanthrone are dissolved at ordinarytemperature, while stirring in 460 parts ofchlorcsulphonic acid. Afterthe addition.

of 51parts oi antimony the temperature is raised vto betweeni) andi.65C.,and dry halogen bromide svpassed intothesolution, As'soon as theweight Vof Vthereaction mixture'has increased by about 35 percentofthedibenzanthrone employed, the re-n action. mixture Vis allowedto cool, 230 parts of concentrated sulphuric` acid, poured into vice-coldv water, and the whole" is boiled for Q a short time andiiltered: by suction. The dyestuffv obtained, a dibromodibenzanthroneaccordel ing toanalysis, is a violet paste, and a blue violet powderwhen dry, dissolving to a red violet solutioninconcentrated sulphuricacid, and dyes cot-v Y ton. excellent fast marine blue [shades fromQa .ltained. Y'

violet-Vat. I

lit/the introduction' of'Y hydrogen bromide be 'continued for -a longerperiod higher brominated products of similar tinctorial properties areob- Sulphur, iodine, mercury and other halogenating catalysts may beemployed instead of anyti pyranthrone in 400 parts of chlorosulphonicacid mony. y

.The Y corresponding brornnated iso-dibenzanthrones are obtained underthe above stated conditions from iso-dibenzanthrone.

Emample 2 20parts of .pyranthrone are dissolved at ordi-lv Anarytemperature, lwhile stirring, in 200 parts'of Vchlorosulr'nhonic acid;thereupon 2 parts of 'sulphur are radded and the'temperature is ,raisedVto C. and dry hydrogen bromide passed into .the solution. Whenv theY.desiredl increasel byV Weight is attained' which, for instance inv thecase of tetra-bromopyranthrone, amounts to per cent calculated on theamount of pyranthrone employed;v the mixture is allowedV to cooll andWorkedup as described in Example 1. The di-Q' triortetra-bromopyranthronesY. obtainable in f ythe aforesaidfmanner dissolvetoa blue solution in concentrated sulphuric acid and dye thev'ege tablefibrevery fast orangetoorange-red shades. By employing lhydrogenchlorideV insteadv of hydrogen bromide the correspondingchloropyranthrones Yare obtained'. I Y

e Example s I ,C vDry. hydrogenbromide is passedinto a solution of 16.6parts of pureY 3.4.8.9-dibenzopyrone- 5.10-quinone Vin 200 parts ofchlorosulphonic Yacid. to which 2 parts of iodine'have been addedat65fC;', until'an increase by weight is obtained diluted withcorresponding to 25"per cent by weight of the said quinone. Thereactionmixture isthen allowed to cool and worked up as described in Example 1,The monobromo3.4.8.9dibenzopyrene-5.10-quinone obtained is anorange-yellowV paste and a yellow-orange powder when dry,v

dissolves to a red-violet solution in concentrated sulphuric acid anddyes cotton from a scarlet vat fast bright,l yellow-orange shades.

Oleum'maybe used as dissolving medium'instead of chlorosulphonic acid.`

When lintroducing n hydrogen bromide for a longer period ottime higherbrominated prod-A ucts are obtained..

- If the isorneric'A `4.5.8.El-dibenzopyrene-B.10- quinonebeemployed-instead of 3.4.8.9-dibenzo4 pyrene-5.10quinone a ldyestuli isobtained dyeing cottonirom an orange-red Vat red shades.

Example 4 2o parts of toluene are introduced, while surring, into asolution of'2 parts of iodine in 100 parts of chlorosulphonic acid whichis -cooled by a mixture .of ice and common salt. Dry hydrogen bromide ispassed into the reactionmixture which is allowed to Warm to between 20and 30 C, As soon as the toluene employed has entered into reactionwhich takes placein a short time, the

reaction mixture is diluted with 50 partsof concentrated sulphuric acid,poured into water and the bromotoluene formed isvseparated. It is a llight colored liquid which does not solidify at 0"A C {and boils between.138 and 140 C., under a vpressure of 15 millimeters ofrmercury. Y ,Di-fand higher brominated derivatives, such as tetra-bromobenzene andhexabromobenzene are obtained4 in a similar manner from benzene..

Naphthalene and phenanthrene, also hydroaro.`

matic compounds, such as hexahydrobenzene';

can be brominated in the Vsaid Way. y

`Eatmnple- 5 24parts of potassium bromide are slowly introduced intoastirred solution of 40 parts of Vtion with sulphuric acid.

The di-bromopyranthrone separating in orange-red flocks is sucked off.The dyestuf dissolves to a bluesolution inv concentrated sulphuricacid'and dyes'cotton orange shades from Va red Violet vat. Y v

Tetrabromopyranthrone is obtained under the stated conditions whenbringing 50 parts 'of potassium bromideY to reaction J Example 6 Y 25,parts of potassium bromidel are introduced at l40 C.] into a stirredsolutionl-ofe parts of di-benzanthrone in'460 parts ofv chlorosulphonicacid to which 0.5 part of antimonyhas been added. Y Afterthe addition ofpotassium bromide the reaction ,mixturer is allowed to warm to between60 and` 65"y C., at which temperature the lreac ti'on mixture ismaintained for about?, hours. The dyestuff 'thus obtained is vworked upin the usual manner and forms a Violet powderldissolving toavioletsolution in sulphuric acid and dyeing cottonvfast marine blueshades froma violet Vat.'

By brominating isodibenzanthrone-under the saine conditions ra dyestuiis-obtained dissolving `to a green solution-fin sulphuricacid and dyeingvegetable bre clear` blue-'violet shades froma violet vat.

"` E:1:am'ple7A azine are dissolved in 450 parts-` of` chlorosul-Aphonic"l acid and the-mixture is 'warmedgwhile stirring,` to between 60and 65 C. after the addi` tion-'o1 2 parts of Yantirnonyand 2 parts ofsulphur, whereupon dry hydrogen bromide is passed intothesolutmn` forseveral hours. f The reaction mixtureis allowed to cool and worked up`in the usual way. The brominated Ndihydro-1,22.1 anthraquinoneazineobtained dyes cotton from a blue vat very Iast blue shades.`-Bromopyridines are'obt'ained frompyridine in an analogousmanner.`Potassium bromideA may be employed'in'stead of hydrogen bromide;

'5. Eixample 8 30 parts of vpotassium bromide'are added, While4stirring, at between 55 and 65 Citoa solution of 33.2"' Aparts of3.4.8.9-dibenzopyrene-104quinone in Y300 parts of chlorosulphonic acidto which 3 parts of iodine have been added. The reaction mixture isstirred at about 65Y to 70 C. until a sample of the reaction productdissolves in concentrated sulphuric acid to a violet-blue solution. Thereaction mixture is then allowed to cool and worked up as usual; Thedibromo- 3.4.8.9-dibenzopyrene-5.10-quinone obtained-is an orange powdercrystallizing in orange needles and dyes cotton excellently fast orangeshades from a violet vat.

When employing the sameilamount of 4.5.8.9- dibenzopyrene-3.l0-quinoneinstead of the aforesaid quinone a `reactionproductdyeing blue-redshades is obtained.4 y

i v vErlcampl'e 9iA l 46 parts of pure dibenzanthrone are dissolved l in460 parts of chlorosulphonic acid. After the addition of 20 parts ofiron sulphate and 4"parts of 'sulphur the reaction mixture is warmed,while stirring, to between r .90 and 100 C. and dry hydrogen chloride ispassed into a solution until a sample ofthe reaction product dissolvesto a vioand.60 ,C..intoa stirred solution of 23,1parts'of benzanthroneinir 200 Aparts of chlorosulphonic acid to whichl2`partsof iodine have`been added. Thereactionmixture is allowed to coolafter several hoursand worked up as usual. The bromobenzanthrone obtained is a yellowpowder crystallizing in needles and dissolving to a red-brown solutionin concentrated sulphuric acid;V

Example 11 45 parts of 5.6.'1.2-diphthaloylacridone are dissolved in 400parts of chlorosulphonic acid and warmedto between `90 and 100 lClafrterthe addi,-

l separating fromthe tion' of vZipartsl of iodine and 2' parts oftantimony. Hydrogen chloride is then passed-into `thestirred solutionuntil a sample of the-reaction product dyes cotton red-orangev shades.'The dy'estuff iso- Vlated in 'thegusual manner dissolves to anf orangesolution in concentrated s'ulphuric acid. Other "acridones may n'beiemployed instead of theaboveLmehtionedV diphthaloylacridone;

In"an"analogous manner the brominated diphthaloylacridone which'dyesstill more reddish,-

orangeshadesA than the'chloroderivatives can be obtained by4 theadditionof .potassium bromide or bythe introduction of hydrogen bromide."Erample 12. Hydrogen iodide is passedint'o'a solution ko1 40 partsr ofpyranthronein400'parts of chlorosull phonicacid, kept at 60 sulphurhavebeen added Y ton by means of a sample of the reaction prod- C., `,towhich 4 parts of uctl indicates the formation of iodopyranvthronj Thedyestui worked up `in-thel usual way fis an orange `powder'dissolving toa blue solution in concentrated sulphuric acid and dyes vegetable shades`of good fastness j l Esvs'ajrnple13,l l I a 30.6 parts ofanthanthroneare dissolved' in7300 parts of a sulphuic acid containingp'e c'ent of sulphur trioxide.

bre from a redi-violet vat strongyellow-lred' until the dyeing` on cot-`17 parts Aof vpotassium'iodide `are- Y introduced during one "hourj intothe `f solution` l maintained at'80o Cs'andthe' iodinationfis finishedbyv heating temperature for-one further hour.y After ycoolingthereaction mass" isfpou'red onto"V ice andthe Vthe reaction mass'j'atthe said FIO productfiltered off, by suction. 'The iodoanthan throneV'obtainedsulphuric `acid vanfd l dyes d cotton orange shades. .fr'omareolvat;v f 'r' 'Example 14 dissolves' to; a green4 solution in Y y iA'30";61parts lof anthanthrone are-convertedinto iodoanthanthroneasdescribed in the. foregoing example and l2. parts of potassium4broxnidevare introduced during one hour into the sulphuric acidsolution containingl sulphur Atrioxide Aat 80"C. which temperature ismaintained for lone further hour tojcomplete the formation of thedyest'ufff. lllhe reaction mixture is thenworked upas usual and-abromoiodoanthanthrone Iobtained* forming an orange-red powder dissolvingto aigreenV sfoluy tion with a bluish tinge in sulphuric acid and dyeingcotton'orangefredshades from a .violet-red vat. The dyestui may; ifdesired, be'tpuried by means of the oxoniumsulphateof the dyestuffdilution with water or gby recrystallization from solvents of high`boilingr point, such as nitroben` zene or trichlorbenzene. p z

sulphuric Vacid Asolution on ,337.6 parts'oi monomethoxyanthanthrondprepared by" treating 4monohydroxyanthanthrone with the methylester oflp-toluene sulphonicacid.

in. .trichlrbenzena arefdissolved ink 330 l, parte 0f i chlorosulphonicacid at 0 C. after an addition of 3 parts of iodine. 20 parts4 ofpotassium bromide are introducedinto the said solution duringone hour,the solution being maintained at 0 "Cffor ordinary temperature.

W5 l one furtherhour and thereaction is completed lat i' Afteronefurther hour, .after dilution with 300 Aparts vof sulphuric acid,

thereaction mass is brought'onto ice and the deposit ltered bysuction'and dried. l. The monov 50,

bromomethoxyanthanthrone obtained is Va red powderv dissolving to agreen solution in concentrated sulphuriceacid and dyes c otton fromaired Yvat'blue yred shades which areexcellently fast againstv light andatmospheric influences,

The monochloro derivativeof monomethoxyanthanthrone obtained in ananalogous manner forms `an orange product readily crystallizing rfromnitrobenzene, dissolves to agreen solution in concentrated sulphuricyacid, and dyes cotton from a redj v at excellently fast orange shades;

Dyestuffs of similar properties are obtained "by employing other Vethersof hydroxy anthanthrone,

for instance ethoxyanthanthrone, omega-chlorethoxyanthanthrone andv thelike instead of Y Y methoxyanthanthrone.

pounds which comprises replacing at leastone hydrogen atom attaching tothe nucleus ofan aromatic compoundby halogen'by acting on the aromaticcompound in an acid selected from the group consisting of oleum,chlorosulphonicacid and mixtures oithese acids', with ahalogenhydride inthe presence of a halogen carrier.

2`. A process-forV halogenating aromatic com pounds which comprisesAreplacing at least one hydrogen atomV aromatic compound byhalogen byactingA on a polynuclear aromatic compound in an acid selected` from thegroup consisting of oleums,j chlorosulphonic acid and mixtures of theseacids,` with arhalogen hydride in the presence of a-halogen carrier. n

3; A process for halogenating aromatic com'- pounds which comprisesVreplacing at least one hydrogen atom attached to the nucleus of anaromatic compound by halogen by acting on a polynuclear aromaticcompound containing a carbonyl group in an acid selectedfrom the-groupconsisting of oleum, chlorosulphonic acid and mixtures of theseacids,.with.a halogen hydride in the presence of a halogen carrier,

4. A process for haloge'nating-V aromatic compoundswhich comprisesreplacing atleast one hydrogen atom attached to the nucleus ofanaromatic compound by halogen `by acting cnav polynuclear aromaticcompound containing a carbonyl group capable of being vatted in an acidselected from thergroup consisting of oleum, chlorosulphonic acid andmixtures of these acids, with a halogen hydride in the presence of ahalogen carrier.

5. A process for halogenating aromatic comdifferent halogen hydrides inthe fp res'enceof a attached to thenucleus of an pounds which comprisesrrreplacingA atr-leastfone hydrogen atom attachedto the-*nucleus `ofanarc- Vmatic compound? by halogen by'acting on an anthanthroneV in .anacid selected'from vvthe group consisting of oleum, chlorosulphonic;acid ,y and mixtures of these acids, with a halogen hydride in thevpresence of a halogen carrier.

6.. A process for: halogenating, l aromatic cornpounds which comprisesyreplacingY several hydrogen atoms attached to the nucleus offan aromaticcompound'aby different halogens by acting on ythe aromatic; compoundinnanv acidselected from the -group :consisting of oleum, chlorosulf`phonicacid and mixtures -of these f acids; with halogen carrier.' y

7. A processv for halogenatingv aromatic vcom-f pounds which jcomprisesreplacing at least one hydrogen atom vattached to the nucleus of. anaromatic'compound byfhalogen byA acting onlthe aro- 9K5 maticcompoundinran acidselected fromgthe group consisting of oleum,chlorosulphonicacid and mixtures of Vthese'acids; With a halogenhy-Vdride in thepresence. of ,a halogen carrier,jthe

halogen hydride-being produced ,within the reaction mixture by theinteractionof the correspond"-V ing alkali metalsalt with the lsaidacid.

8i 4As s new articles of manufacture monohalogen'r derivatives. off thecompound corresponding tothe- 1f ormula: Y 105 in which R stands for analkyl'groupwhich'may be substituted by halogene v v 9. Asrnew articlesof manufacture monobromo derivatives ofN the" compounds correspondingkto tlie formular'V l in which R stands for an alkyl group whichmay besubstituted by=halogenf 10. As a new article jofl manufacturemonobromo-monomethoxyanthanthrone forming a redpowder,` dissolving to agreen solution in concentrated :,sulphuricfr acid.; and. dyeing cottonex? Ycellent'fast bluishred Vshades from' ajredlvatiVIV A. MAXALBERTVKUNZL.

KARLKOEBERLE. v ERICH; BERTHOLD:

